Probe for NMR apparatus using magnesium diboride

ABSTRACT

To provide a probe coil for an NMR apparatus which can transmit and receive high frequency radio waves with improved Q-factor and S/N ratio. As a measure, the probe coil for an NMR apparatus is provided as of a solenoid type formed of magnesium diboride superconductor. As another measure, the probe coil for an NMR apparatus has a plurality of coils using magnesium diboride superconductors connected in series. As further another measure, there is used a magnesium diboride superconductor mixed with metal. As still further another measure, the probe coil for an NMR apparatus is formed by using a single metal selected from gold, silver, copper, aluminum, iron, platinum, palladium, nickel, stainless steel, chromium, magnesium, tantalum, niobium, titanium, zinc, beryllium, tungsten, or cobalt, or an alloy including a plurality thereof.

The present application is a continuation of Application No. 10/383,655filed, Mar. 10, 2003 (now U.S. Pat. No. 6,967,482), which is acontinuation of 10/315,115, filed Dec. 10, 2002 (now U.S. Pat. No.6,768,306), the entire disclosures of which are incorporated herein byreference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a probe coil for a nuclear magneticresonance apparatus.

2. Description of the Related Art

In general, in an NMR apparatus, there exist a CW type in which a sampleis irradiated by an electromagnetic wave of radio frequency signal witha fixed frequency, and a pulse Fourier type in which a sample isirradiated by a pulse-like electromagnetic wave. Recently, however, thelatter pulse Fourier type NMR has been often referred to as an NMRapparatus. In the specification in the application, the pulse Fouriertype NMR apparatus is to be normally referred to as a nuclear magneticresonance apparatus.

A fundamental arrangement about an NMR apparatus is described in “PartIII, Measuring Technology” in “NMR no sho (The book of NMR)”, by YojiArada, Maruzen, 2000. According to the reference, the NMR apparatus isarranged with a superconducting magnet that generates a static magneticfield, a probe that is provided with a probe coil therein forirradiating a sample contained inside with a high frequency pulsedmagnetic field and for receiving a free induction decay signal (FIDsignal) transmitted from the sample, a high frequency power source thatsupplies a high frequency current to the probe, an amplifier thatamplifies the free induction decay signal, a detector that detects thesignal, and an analyzing unit that analyzes the signal detected by thedetector. About the probe coil, there is a probe provided with aplurality of coils for being applicable to various nuclides andmeasuring methods. Moreover, the probe coil normally has a function ofirradiating a sample with a high frequency pulsed magnetic fieldtogether with a function of receiving a free induction decay signaltransmitted from the sample.

In a current common NMR, a probe is formed in a saddle type. Accordingto the above-described “The book of NMR”, in the case of the saddlecoil, the high frequency pulsed magnetic field, i.e., an RF magneticfield, is directed perpendicularly to the direction of the axis of thecoil. Hence, when a static magnetic field is provided to directperpendicularly, the saddle coil wound around a perpendicularly setsample tube permits measurement with an RF magnetic field applied in thedirection perpendicular to that of the static magnetic field.

Meanwhile, there also exists a solenoid type as a form of the probe. Inthe case of the solenoid coil, an RF magnetic field is directed inparallel with the direction of the axis of the coil. This, for anarrangement in which the solenoid coil is wound around a sample tube,necessitates the static magnetic field to be applied perpendicularly tothe direction of the axis of the coil, i.e., in the horizontaldirection. According to the above-described “The book of NMR”, in thecase of the solenoid coil, because of its easiness in impedance control,a value of a Q-factor, which determines a sharpness in tuning the coil,is enhanced more easily compared with the saddle coil. Furthermore,according to D. I. Hoult and R. E. Richards, “The Signal-to-Noise Ratioof the Nuclear Magnetic Resonance Experiment”, J. Magn. Resonance 24,71–85 (1976), comparison of probe coils having typical arrangementspresented that the solenoid coil has calculated performance about threetimes higher than that of the saddle coil.

From the foregoing, it has been proved that the form of the probe coilis more preferable in the solenoid type. However, at present, anapparatus in which a vertical static magnetic field is generated by thesuperconducting magnet is dominant, and most of the NMR apparatus employthe saddle type probe coils. The reason for this is: (1) For employingthe solenoid type probe coil, a sample tube and a center bore of thesuperconducting magnet for generating a static magnetic field must bedisposed orthogonal to each other, which necessitates the size of thesample tube to be made small; (2) There is necessity of enlarging thediameter of the center bore of the superconducting magnet, which makesthe design of the superconducting magnet difficult; or the like.

Meanwhile, as a measure for improving an S/N ratio, a low-temperatureprobe (cryoprobe) is sometimes used. According to the above-described“The book of NMR”, the low-temperature probe is referred to as a probewith a system in which a circuit about the probe is made superconductingwith the inside of the probe including a preamplifier cooled by lowtemperature helium gas of the order of 20K. As a superconductortherefor, an oxide superconductor is used.

The low temperature probe has two advantages. One is a capability ofenhancing a Q-factor of the coil because of lowered electric resistanceof the circuit. The value of Q as the Q-factor of the coil is expressedby the following equation (1):

$\begin{matrix}{Q = {\sqrt{\frac{L}{C}}\frac{1}{R}}} & (1)\end{matrix}$where L is inductance, C is capacitance, and R is resistance. Accordingto the equation (1), it is understood that the Q as the Q-factor isenhanced as the electric resistance R is decreased. The other isimprovement in the S/N ratio due to lowered temperature which couldreduced thermal noise of the whole circuit. A noise voltage V_(n) can beexpressed by the following equation (2):V _(n)=√{square root over (4kTΔfR)}  (2)where k is Boltzmann constant, T is temperature, Δf is bandwidth, and Ris electric resistance. According to the equation (2), it is understoodthat the noise voltage V_(n) becomes small as the temperature T islowered. Moreover, in common metal, as the temperature T is lowered, theelectric resistance R becomes small. Therefore, by cooling the probe tobe made superconducting, the noise voltage V_(n) can be made reducedwith a rate more than a rate proportional to R to the one-half power.

Moreover, as a technology relating to the above technology, one isdescribed in Japanese Patent Laid-Open No. 133127/1999 which, forreducing thermal noise at reception, employs a birdcage type probe coilusing a superconductor cooled at a low temperature to improve S/N ratio.In this case, high-temperature superconductive material such as YBCO(YBa₂Cu₃O_(7−x), yttrium series high-temperature superconductor) isused. The superconductor is applied to only a linear section of thebirdcage type coil.

As explained above, by the solenoid type probe coil and thelow-temperature probe, there is expected considerable improvement inperformance. However, when a low-temperature probe using oxidesuperconductor is to be applied as a solenoid type probe coil, therearise problems as explained below. (1) An oxide superconductor commonlyused in the low-temperature probe is a thin film conductor of YBCO whichis difficult to be formed in shapes other than that of a linearconductor with a current technology. In addition, (2) Oxidesuperconductors including YBCO have a strong relationship between adirection of a magnetic field and a transport current, i.e. haveso-called strong magnetic field direction dependence of the transportcurrent, and it is known in the thin film conductor that the criticalcurrent is extremely reduced when the magnetic field acts in thedirection orthogonal to the film plane. As in the above, it has beendifficult up to now to make a probe coil with a complicated form tooffer a problem that application to the solenoid type probe coil isdifficult. Furthermore, even when using other kinds of superconductors,in a conventional superconductor wire such as a powder-in-tubesuperconductor wire or a superconductor wire with external stabilizingmaterial formed by conventional extrusion, or a superconductor wire inwhich a superconductor is formed on a metal substrate of a good electricconductor, the metal provided around the superconductor resulted infunctioning as an electromagnetic shield. This has caused a problem ofmaking it impossible to transmit and receive high frequency radio waves.

SUMMARY OF THE INVENTION

Accordingly, it is an object of the invention to provide a probe coilfor an NMR apparatus which can transmit and receive high frequency radiowaves with improved Q-factor and S/N ratio.

As was reported in Nature, 410, 63–64 (2001), it has been found thatmagnesium diboride (MgB₂) exhibits superconductivity. Characteristics ofMgB₂ are shown as follows. The critical temperature of MgB₂ is 39K. Thisis the maximum value of those of conventional metallic superconductivematerials. The critical magnetic field at 0K is about 18 T. This belongsto the group of high values compared with values of conventionalmetallic superconductive materials. The inventors, giving attention togood properties of MgB₂ as a superconductor, have continued studying asto whether it is possible or not to apply MgB₂ to the low-temperatureprobe coil in a solenoid shape NMR. As a result of studying, it has beenascertained that MgB₂ crystal powders are compressed to be capable ofpassing through a superconductive current and to be capable of beingmade into shapes other than the linear shape, and that no magnetic fielddirection dependence of the transport current is observed in thus madesuperconductors. In addition, it has been made certain that realizationof the solenoid-shaped probe coil is possible without enclosing thesuperconductor by metal.

In order to achieve the above-described object on the basis of the abovefindings, the inventors have employed measures as follows.

First, as a first measure of achieving the above object, asuperconductor using a magnesium diboride superconductor is used for aprobe coil for an NMR apparatus. This enables realization of a probecoil for an NMR apparatus with improved Q-factor and S/N ratio.

Moreover, as a second measure, it is characterized that the probe coilfor an NMR apparatus in the first measure is of a saddle type.

In addition, as a third measure, it is characterized that the probe coilfor an NMR apparatus in the first measure is of a solenoid type with thecenter axis thereof being orthogonal to the above-described uniformstatic magnetic field.

In addition, as a fourth measure, the probe coil for an NMR apparatus inany one of the first to third measures is characterized in that themagnesium diboride superconductor is exposed on an outer surface of theabove-described probe coil for an NMR apparatus.

In addition, as a fifth measure, the probe coil for an NMR apparatus inany one of the first to third measures is characterized by having aceramic insulation layer in which the magnesium diboride includessilicon oxide or aluminum oxide. This enables realization of a probecoil for an NMR apparatus with a high insulating performance.

In addition, as a sixth measure, it is characterized that, in the fourthor the fifth measure, a cross section of the probe coil for an NMRapparatus is a rectangular or a circular cross section.

In addition, as a seventh measure, a probe coil for an NMR apparatus ischaracterized in that a plurality of coils using magnesium diboridesuperconductors are connected in series.

In addition, as an eighth measure, it is characterized that, in theseventh measure, the coil using magnesium diboride superconductor is ofa solenoid type with the center axis thereof being orthogonal to theabove-described uniform static magnetic field.

In addition, as a ninth measure, it is characterized that, in theseventh or the eighth measure, a plurality of the coils are connected byusing a material including magnesium diboride.

In addition, as a tenth measure, it is characterized that a magnesiumdiboride superconductor mixed with metal is used for the probe coil foran NMR apparatus. This enables realization of a probe coil for an NMRapparatus that can accelerate decay of high frequency pulses by anadequate electric resistance of the coil.

In addition, as a eleventh measure, it is characterized that the probecoil for an NMR apparatus is formed by using a single metal selectedfrom gold, silver, copper, aluminum, iron, platinum, palladium, nickel,stainless steel, chromium, magnesium, tantalum, niobium, titanium, zinc,beryllium, tungsten, or cobalt, or an alloy including a pluralitythereof.

Furthermore, as a twelfth measure, it is characterized that the probecoils for the NMR apparatus in the first to eleventh measures are usedfor the NMR apparatus.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a view showing a saddle type probe coil for an NMR apparatus.

FIG. 2 is a block diagram of an NMR probe and an NMR signal measuringsystem.

FIG. 3 is a view showing a solenoid type probe coil for an NMRapparatus.

FIG. 4 is a view showing a rectangular section reinforcing memberincluding type magnesium diboride superconducting wire.

FIG. 5 is a view showing a circular section reinforcing member includingtype magnesium diboride superconducting wire.

FIG. 6 is a view showing a tape type magnesium diboride superconductingwire.

FIG. 7 is a view showing a rectangular section reinforcing memberincluding type magnesium diboride superconducting wire with aninsulation layer.

FIG. 8 is a view showing a circular section reinforcing member includingtype magnesium diboride superconducting wire with an insulation layer.

FIG. 9 is a view showing a tape type magnesium diboride superconductingwire with an insulation layer.

FIG. 10 is a view showing a superconductive connection type solenoidtype probe coil for an NMR apparatus.

FIG. 11 is a block diagram of an NMR probe and an NMR signal measuringsystem applicable to multi-nuclides.

DESCRIPTION OF THE PREFERRED EMBODIMENTS EXAMPLE 1

A saddle type probe coil for an NMR apparatus according to Example 1 isshown in FIG. 1. FIG. 1 illustrates main points of the invention.

A coil 1 is disposed outside a glass sample tube 3 with a shape in whichcoils, each known as a so-called saddle coil, are arranged opposite toeach other. In the glass sample tube 3, there is contained a sample tobe measured 4. The material of the coil 1 is a superconducting wire ofmagnesium diboride. In FIG. 1, the coil 1 is formed with two one-turnsaddle coils. With the two saddle coils having the same shapes and thesame number of turns, it is possible to employ arbitrary shape andnumber of turns. To both ends of the coil 1, a current lead 5 a and acurrent lead 5 b, being copper wires, are connected by solderingrespectively. When a direct current is supplied between the current lead5 a and the current lead 5 b, each of the saddle coils generates amagnetic field in the direction 6 of an arrow in FIG. 1. Therefore, atthe center of the sample 4, a uniform magnetic field can be generated inthe direction 6 of the arrow. These structural elements are put in thehigh uniform static magnetic field generated by a superconductingmagnet. The direction of the high static magnetic field in this casebecomes that indicated in the direction 2.

The coil 1 may be wound around a coil bobbin. The coil bobbin, however,is required to have relative permeability close to 1, that is, to be amaterial with permeability thereof close to that of vacuum so as not tocause disturbance of the high uniform static magnetic field. Moreover,since the coil 1 is supplied with a high frequency pulsed current toapply a high frequency pulsed magnetic field to the sample to bemeasured 4, the coil bobbin is further required to be an insulator thatdoes not shield the high frequency magnetic field. Furthermore, when thecoil bobbin is provided as that including a nuclide to be measured, thecoil bobbin itself generates an NMR signal to make it impossible todistinguish the NMR signal from an NMR signal transmitted from thesample to be measured 4. Thus, care is required in selecting thematerial. Therefore, a special glass including components for adjustingpermeability is desirable for the coil bobbin. In addition, theabove-described special glass is desirable not only for the coil bobbinbut also for the sample tube 3 and, although not shown in FIG. 1,constituents of a vacuum insulating layer provided outside of the sampletube 3.

In FIG. 2, there is shown a block diagram of an NMR probe and an NMRsignal measuring system in the NMR apparatus in this Example. A probe107 is provided with inside thereof the coil 1, a capacitor 108, and thelike. The coil 1 is cooled at about 20K or below. Desirable coolingmethods are a method of immersing the coil 1 in liquid helium (poolcooling method), a method of externally supplying gaseous helium (gascooling method), a method of circulating gaseous, liquid, orsupercritical helium by an external compressor (forced cooling method),a method of cooling by heat conduction by using a compact GMrefrigerator (refrigerator cooling method), and the like.

In addition, although not shown specifically in FIG. 2, the probe 107 isdisposed in a uniform static magnetic field generated by asuperconducting magnet. To the coil 1, a high frequency pulsed current,generated at a high frequency power source 101 and amplified by a poweramplifier 102, is applied through the current leads 5 a and 5 b. Thefrequency can be calculated from the static magnetic field and agyromagnetic ratio of a nuclide to be measured. For example, when aproton is measured in a static magnetic field of 2.35 T, the frequencyis given as 100 MHz. The pulse width, although depending on theintensity of the magnetic field generated by the coil 1, is given asbeing approximately several μs to several tens of μs. The electric powerrequired for the high frequency pulsed current is commonly several tensof watts to several hundreds of watts. The high frequency pulsed currentcan be generated with arbitrary frequency, pulse width, and sequence bya controller 100.

An operation of the NMR apparatus according to this Example will beexplained. When the high frequency pulsed current is passed through thecoil 1, a high frequency pulsed magnetic field is applied to the sampleto be measured 4 in the sample tube 3. When the sample to be measured 4includes nuclides that produce nuclear magnetic resonance, the nuclearmagnetic resonance of each of the nuclides produces a free inductiondecay (FID) signal to be transmitted after the application of the highfrequency pulsed current is ceased. The free induction decay signal isreceived by the coil 1. The received signal is amplified by apreamplifier 103 and a signal amplifier 104. The preamplifier 103 iscooled down to about 80K for reducing noise. The cooling method thereofis desirably the same as the cooling method of the coil 1. However, in amethod of using refrigerant, the refrigerant can be nitrogen rather thanhelium. Moreover, when the preamplifier can be set in an environmentwith sufficiently small noise, no cooling is necessary for thepreamplifier 103. The free induction decay signal amplified in the twostage amplifiers is detected by a detector 105 to become a signal with abandwidth of several kHz. Further, the signal is expanded in Fourierseries to be subjected to data analysis in a signal-analyzing unit 106,by which an NMR spectrum can be obtained. There are many more peripheralunits than those explained above, which are, however, omitted in FIG. 2.

The inventors carried out manufacturing of the probe for an NMRapparatus as described above. The coil 1 as a saddle type has a diameterof 2 cm for a circular arc section and a length of 5 cm for a linearsection with a number of turn of each of the saddle coils provided asbeing one turn. The coil 1 was cooled at about 10K by a gas coolingmethod using gaseous helium and the preamplifier 103 was cooled at about77K by a pool cooling method using liquid nitrogen. The probe for an NMRapparatus as described above was disposed in a high uniform staticmagnetic field of 2.35 T to measure an NMR spectrum of proton in ethanolby using a high frequency power source of 100 MHz as the resonantfrequency of proton. Besides, as a comparative example, a probe with thecoil 1 made of copper was also manufactured for measuring the NMRspectrum of proton with the coil 1 and the preamplifier 103 kept at roomtemperature without being cooled. As a result of a series of tests,about the S/N ratio, it was ascertained that the probe using a magnesiumdiboride superconductor wire for the coil 1 was superior about fivetimes to the probe using copper. Furthermore, it was also ascertainedthat the probe using magnesium diboride superconductor wire was superiorabout ten times in Q-factor.

As was described above, by using the superconductor made of magnesiumdiboride superconductor for a probe coil, realization of a probe coilfor an NMR apparatus has been made possible with improved Q-factor andS/N ratio.

EXAMPLE 2

A solenoid type probe coil for an NMR apparatus according to Example 2is shown in FIG. 3.

Each coil 1 is disposed outside a glass sample tube 3 with a shape knownas a so-called solenoid coil. In the glass sample tube 3, there iscontained a sample to be measured 4. The coil 1 is formed with asuperconducting wire of magnesium diboride. To both ends of the coil 1,a current lead 5 a and a current lead 5 b, being copper wires, areconnected by soldering, respectively, by which an arrangement isprovided so that, when a direct current is supplied between the currentlead 5 a and the current lead 5 b, a uniform magnetic field can begenerated in the direction 6 of an arrow at the center of the sample 4.These structural elements are put in the high uniform static magneticfield generated by a superconducting magnet. The direction of the highstatic magnetic field in this case is indicated in the direction 2perpendicular to the sheet. The coil 1 may be wound around a coilbobbin. The coil bobbin, however, is required to have relativepermeability close to 1, that is, to be a material with permeabilitythereof close to that of vacuum so as not to cause disturbance of thehigh uniform static magnetic field. Moreover, since the coil 1 issupplied with a high frequency pulsed current to apply a high frequencypulsed magnetic field to the sample to be measured 4, the coil bobbin isfurther required to be an insulator that does not shield the highfrequency magnetic field. Furthermore, when the coil bobbin is providedas that including a nuclide to be measured, the coil bobbin itselfgenerates an NMR signal to make it impossible to distinguish the NMRsignal from an NMR signal transmitted from the sample to be measured 4.Thus, care is required in selecting the material. Therefore, a specialglass including components for adjusting permeability is desirable forthe coil bobbin. In addition, the above-described special glass isdesirable not only for the coil bobbin but also for the sample tube 3and, although not shown in FIG. 3, constituents of a vacuum insulatinglayer provided outside of the sample tube 3.

By using FIG. 2 again, explanations will be made about an NMR probe andan NMR signal measuring system in the NMR apparatus in this Example.

A probe 107 is provided with inside thereof the coil 1, a capacitor 108,and the like. The coil 1 is cooled at about 20K or below. Desirablecooling methods are a method of immersing the coil 1 in liquid helium(pool cooling method), a method of externally supplying gaseous helium(gas cooling method), a method of circulating gaseous, liquid, orsupercritical helium by an external compressor (forced cooling method),a method of cooling by heat conduction by using a compact GMrefrigerator (refrigerator cooling method), and the like. Although notshown specifically in FIG. 2, the probe 107 is disposed in a uniformstatic magnetic field generated by a superconducting magnet. To the coil1, a high frequency pulsed current, generated at a high frequency powersource 101 and amplified by a power amplifier 102, is applied throughthe current leads 5 a and 5 b. The frequency can be calculated from thestatic magnetic field and a gyromagnetic ratio of a nuclide to bemeasured. For example, when a proton is measured in a static magneticfield of 2.35 T, the frequency is given as 100 MHz. The pulse width,although depending on the intensity of the magnetic field generated bythe coil 1, is given as being approximately several μs to several tensof μs. The electric power required for the high frequency pulsed currentis commonly several tens of watts to several hundreds of watts. The highfrequency pulsed current can be generated with arbitrary frequency,pulse width, and sequence by a controller 100.

When the high frequency pulsed current is passed through the coil 1, ahigh frequency pulsed magnetic field is applied to the sample to bemeasured 4 in the sample tube 3. When the sample to be measured 4includes nuclides that produce nuclear magnetic resonance, the nuclearmagnetic resonance of each of the nuclides produces a free inductiondecay (FID) signal to be transmitted after the application of the highfrequency pulsed current is ceased. The free induction decay signal isreceived by the coil 1. The received signal is amplified by a:preamplifier 103 and a signal amplifier 104. The preamplifier 103 iscooled down to about 80K for reducing noise. The cooling method thereofis desirably the same as the cooling method of the coil 1. However, in amethod of using refrigerant, the refrigerant can be nitrogen rather thanhelium. Moreover, when the preamplifier can be set in an environmentwith sufficiently small noise, no cooling is necessary for thepreamplifier 103. The free induction decay signal amplified in the twostage amplifiers is detected by a detector 105 to become a signal with abandwidth of several kHz. Further, the signal is expanded in Fourierseries to be subjected to data analysis in a signal-analyzing unit 106,by which an NMR spectrum can be obtained. There are many more peripheralunits than those explained above, which are, however, omitted in FIG. 2.

The inventors carried out manufacturing of the probe for an NMRapparatus as described above. The coil 1 as a solenoid type has adiameter of 2 cm and a longitudinal length of 5 cm with a number ofturns of the coil 1 provided as being 10 turns. The coil 1 was cooled atabout 10K by a gas cooling method using gaseous helium and thepreamplifier 103 was cooled at about 77K by a pool cooling method usingliquid nitrogen. The probe for an NMR apparatus as described above wasdisposed in a high uniform static magnetic field of 2.35 T to measure anNMR spectrum of proton in ethanol by using a high frequency power sourceof 100 MHz as the resonant frequency of proton. Besides, as acomparative example, a probe with the coil 1 made of copper was alsomanufactured for measuring the NMR spectrum of proton with the coil 1and the preamplifier 103 kept at room temperature without being cooled.As a result of a series of tests, about the S/N ratio, it wasascertained that the probe using a magnesium diboride superconductorwire for the coil 1 was superior about five times to the probe usingcopper. Furthermore, it was also ascertained that the probe usingmagnesium diboride superconductor wire was superior about twenty timesin Q-factor.

As was described above, by using the superconductor made of magnesiumdiboride superconductor for a probe coil, realization of a probe coilfor an NMR apparatus has been made possible with improved Q-factor andS/N ratio. Furthermore, the values were improved ones compared withthose in Example 1 to have enabled realization of a probe coil fur theNMR apparatus with further higher performances by providing the form ofthe coil as being the solenoid type.

EXAMPLE 3

In FIG. 4, there is shown the case of using a magnesium diboridesuperconducing wire for the probe coil for the NMR apparatus in Example3. Except for the arrangement, this Example is almost the same asExample 2.

The magnesium diboride superconducing wire has the magnesium diboridesuperconductor 11 exposed on an outer surface of the wire with areinforcing member 13 to be a supporting member disposed inside. Themagnesium diboride superconductor 11 can be used as a green compact forwhich material powders are compressed, a sintered compact solidified byheat treatment, a crystalline solid grown on the reinforcing member byCVD etc., and the like. For the reinforcing member 13, there can be useda metal such as copper, aluminum, nickel, or silver, an alloy such asstainless steel, copper alloy, a metallic super conductor such asniobium-titanium, a carbon fiber, a boron fiber, ceramics such asalumina or silica, or the like. Moreover, when it can be judged that thesuperconducting wire has enough strength to require no reinforcingmember 13, no reinforcing member 13 can be necessary. Furthermore,although the magnesium diboride superconducting wire in FIG. 4 has arectangular cross section, the cross section can be a circular one asshown in FIG. 5 or that in which a magnesium diboride thin film isformed on the surface of the reinforcing member 13 as shown in FIG. 6.Each of the magnesium diboride superconducting wires in FIG. 4, FIG. 5,and FIG. 6 has a structure of a single core wire with a singlesuperconductor. For the wire, however, there can be used a multi-corewire with a structure in which a plurality of superconducting wires arebundled. The superconducting wire with a structure of being thus exposedon the outersurface of the probe coil for an NMR apparatus causes lessattenuation of the high frequency magnetic field on the peripheralsection compared with such a superconducting wire as to have a metalperiphery. This enables efficient irradiation with a high frequencymagnetic field and reception of an FID signal.

The inventors carried out manufacturing of the probe for an NMRapparatus as described above. The coil 1 as a solenoid type has adiameter of 2 cm and a longitudinal length of 5 cm with a number ofturns of the coil 1 provided as being 10 turns. The coil 1 was cooled atabout 10K by a gas cooling method using gaseous helium and thepreamplifier 103 was cooled at about 77K by a pool cooling method usingliquid nitrogen. The probe for an NMR apparatus as described above wasdisposed in a high uniform static magnetic field of 2.35 T to measure anNMR spectrum of proton in ethanol by using a high frequency power sourceof 100 MHz as the resonant frequency of proton. Besides, as acomparative example, a probe with the coil 1 made of copper was alsomanufactured for measuring the NMR spectrum of proton with the coil 1and the preamplifier 103 kept at room temperature without being cooled.As a result of a series of tests, about the S/N ratio, it wasascertained that the probe using a magnesium diboride superconductorwire for the coil 1 was superior about six times to the probe usingcopper. Furthermore, it was also ascertained that the probe usingmagnesium diboride superconductor wire was superior about twenty-fivetimes in the Q-factor.

As was described above, by using for a probe coil the superconductorwire with the magnesium diboride superconductor 11 exposed on thesurface thereof, realization of a probe coil for an NMR apparatus hasbeen made possible with improved Q-factor and S/N ratio. Furthermore, byusing the superconducting wire with magnesium diboride provided around,the values of the Q-factor and the S/N ratio were improved ones even inthe comparison with those in Example 1 to have enabled realization of aprobe coil for the NMR apparatus with further higher performances.

EXAMPLE 4

In FIG. 7, there is shown an example of using a magnesium diboridesuperconducing wire for the probe coil for the NMR apparatus in Example4. Except for the arrangement, this Example is almost the same asExample 2.

The magnesium diboride superconducing wire has an insulation layer 12 ofsilicon oxide or aluminum oxide on a surface of the wire with themagnesium diboride superconductor 11 and a reinforcing member 13 to be asupporting member disposed inside thereof. The magnesium diboridesuperconductor 11 can be used as a green compact for which materialpowders are compressed, a sintered compact solidified by heat treatment,a crystalline solid grown on the reinforcing member by CVD, etc., andthe like. For the reinforcing member 13, there can be used a metal suchas copper, aluminum, nickel, or silver, an alloy such as stainlesssteel, copper alloy, a metallic super conductor such asniobium-titanium, a carbon fiber, a boron fiber, ceramics such asalumina or silica, or the like. Moreover, when it can be judged that thesuperconducting wire has enough strength to require no reinforcingmember 13, no reinforcing member 13 can be necessary. Furthermore,although the magnesium diboride superconducting wire in FIG. 7 has arectangular cross section, the cross section can be a circular one asshown in FIG. 8 or that in which a magnesium diboride thin film isformed on the surface of the reinforcing member 13 as shown in FIG. 6with an insulation layer 12 further provided thereon. Each of themagnesium diboride superconducting wires in FIG. 7, FIG. 8, and FIG. 6has a structure of a single core wire with a single superconductor. Forthe wire, however, there can be used a multi-core wire with a structurein which a plurality of superconducting wires are bundled. Thesuperconducting wire with such a structure, having an insulator formedaround, causes less attenuation of the high frequency magnetic field onthe peripheral section compared with such a superconducting wire as tohave a metal periphery. This enables not only efficient irradiation witha high frequency magnetic field and reception of an FID signal but alsoimprovement in withstand voltage.

The inventors carried out manufacturing of the probe for an NMRapparatus as described above. The coil 1 as a solenoid type has adiameter of 2 cm and a longitudinal length of 5 cm with a number ofturns of the coil 1 provided as being 10 turns. The coil 1 was cooled atabout 10K by a gas cooling method using gaseous helium and thepreamplifier 103 was cooled at about 77K by a pool cooling method usingliquid nitrogen. The probe for an NMR apparatus as described above wasdisposed in a high uniform static magnetic field of 2.35 T to measure anNMR spectrum of proton in ethanol by using a high frequency power sourceof 100 MHz as the resonant frequency of proton. As a result of a seriesof tests, it was ascertained that the probe was almost equivalent to theprobe shown in Example 3 about the S/N ratio and the Q-factor, but thewithstand voltage was improved by a hundred times.

As was described above, by using for a probe coil the insulation layeraround the superconductor wire with the magnesium diboridesuperconductor 11 exposed on the surface thereof, realization of a probecoil for an NMR apparatus has been made possible with an improvedwithstand voltage.

EXAMPLE 5

A solenoid type probe coil for an NMR apparatus according to Example 5is shown in FIG. 10. Except for this, this Example is almost the same asExample 4.

As shown in FIG. 10, coils 1 a, 1 b, and 1 c are connected in serieselectrically. At connections, two magnesium diboride superconductorwires, after insulation layers thereof being removed, are brought intosuperconductive connection through magnesium diboride superconductivepowders to provide electric resistance of the coils connected in seriesas being almost zero at or below the critical temperature. Theconnection is desirably provided by a method of lapping two magnesiumdiboride superconductor wires over a distance of several centimeterswith insulation layers thereof being removed (lap connection method) ora method of getting cross sections of the connections butted againsteach other (butt connection method). Moreover, for bringing electricresistance close to zero, the connection is desirably provided throughthe magnesium diboride superconductor. With structures thus prepared,even in the case in which it is difficult to integrally form the coil,by connecting divided coils later, the whole electric resistance can bebrought close to zero. Therefore, according to the expression 1 and theexpression 2, it becomes possible to improve Q-factor and S/N ratio.

To both ends of the coil 1 a, a current lead 5 a and a current lead 5 b,being copper wires, are connected by soldering, respectively. Moreover,to the other end of the coil 1 b and to the other end of the coil 1 c, acurrent lead 5 c and a current lead 5 d are connected by soldering,respectively. By thus providing a number of current leads, it becomespossible to determine an intensity of a generated magnetic field and aninductance depending on resonant frequency of a nuclide as a subject tobe measured. For example, application of a high frequency pulsed currentbetween the 5 a and 5 b for ¹H, and that between 5 c and 5 d for ¹³C,enable matching the resonant frequency and the inductance to each of thenuclide as the subjects to be measured. Incidentally, in this Example,although the current leads were connected to the connections of thecoils 1 a, 1 b, and 1 c, the connections are not limited to those, butmay be provided at any arbitrary points of the coils.

The structural elements explained above are, in an NMR probe, put in thehigh uniform static magnetic field generated by a superconductingmagnet. The direction of the high static magnetic field in this case isindicated in the direction 2 perpendicular to the sheet.

In FIG. 11, there is shown a block diagram of an NMR probe and an NMRsignal measuring system in the NMR apparatus in this Example. A probe107 is provided with inside thereof the coils 1 a, 1 b and 1 c,capacitors 108 and 118, and the like. The coils 1 a, 1 b and 1 c arecooled at about 20K or below. Desirable cooling methods are a method ofimmersing the coils 1 a, 1 b and 1 c in liquid helium (pool coolingmethod), a method of circulating gaseous, liquid, or supercriticalhelium by an external compressor (forced cooling method), a method ofcooling by heat conduction by using a compact GM refrigerator(refrigerator cooling method), and the like. Although not shownspecifically in FIG. 11, the probe 107 is disposed in a uniform staticmagnetic field generated by a superconducting magnet. To the coil 1 a, ahigh frequency pulsed current, generated at a high frequency powersource 101 and amplified by a power amplifier 102, is applied throughthe current leads 5 a and 5 b. The frequency can be calculated from thestatic magnetic field and a gyromagnetic ratio of a nuclide to bemeasured. For example, when a proton is measured in a static magneticfield of 2.35 T, the frequency is given as 100 MHz. The pulse width,although depending on the intensity of the magnetic field generated bythe coil 1 a, is given as being approximately several μs to several tensof μs. The electric power required for the high frequency pulsed currentis commonly several tens of watts to several hundreds of watts. The highfrequency pulsed current can be generated with arbitrary frequency,pulse width, and sequence by a controller 100. When the high frequencypulsed current is passed through the coil 1 a, a high frequency pulsedmagnetic field is applied to the sample to be measured 4 in the sampletube 3. When the sample to be measured 4 includes nuclides that producenuclear magnetic resonance, the nuclear magnetic resonance of each ofthe nuclides produces a free induction decay (FID) signal to betransmitted after the application of the high frequency pulsed currentis ceased. The free induction decay signal is received by the coil 1 a.The received signal is amplified by a preamplifier 103 and a signalamplifier 104. The preamplifier 103 is cooled down to about 80K forreducing noise. The cooling method thereof is desirably the same as thecooling method of the coil 1. However, in a method of using refrigerant,the refrigerant can be nitrogen rather than helium. Moreover, when thepreamplifier can be set in an environment with sufficiently small noise,no cooling is necessary for the preamplifier 103. The free inductiondecay signal amplified in the two stage amplifiers is detected by adetector 105 to become a signal with a bandwidth of several kHz.Further, the signal is expanded in Fourier series to be subjected todata analysis in a signal-analyzing unit 106, by which an NMR spectrumcan be obtained. There are many more peripheral units than thoseexplained above, which are, however, omitted in FIG. 11.

Meanwhile, to a coil in which the coil 1 b, 1 a and 1 c are connected inseries, a high frequency pulsed current, generated at a high frequencypower source 111 and amplified by a power amplifier 112, is appliedthrough the current leads 5 c and 5 d. The frequency can be calculatedfrom the static magnetic field and a gyromagnetic ratio of a nuclide tobe measured. For example, when ¹³C is measured in a static magneticfield of 2.35 T, the frequency is given as 15 MHz. The pulse width,although depending on the intensity of the magnetic field generated bythe coil in which the coil 1 b, 1 a and 1 c are connected in series, isgiven as being approximately several μs to several tens of μs. Theelectric power required for the high frequency pulsed current iscommonly several tens of watts to several hundreds of watts. The highfrequency pulsed current can be generated with arbitrary frequency,pulse width, and sequence by a controller 110.

When the high frequency pulsed current is passed through the coil inwhich the coil 1 b, 1 a and 1 c are connected in series, a highfrequency pulsed magnetic field is applied to the sample to be measured4 in the sample tube 3. When the sample to be measured 4 includesnuclides that produce nuclear magnetic resonance, the nuclear magneticresonance of each of the nuclides produces a free induction decay (FID)signal to be transmitted after the application of the high frequencypulsed current is ceased. The free induction decay signal is received bythe coil in which the coil 1 b, 1 a and 1 c are connected in series. Thereceived signal is amplified by a preamplifier 113 and a signalamplifier 114. The preamplifier 113 is cooled down to about 80K forreducing noise. The cooling method thereof is desirably the same as thecooling method of the coil 1. However, in a method of using refrigerant,the refrigerant can be nitrogen rather than helium. Moreover, when thepreamplifier can be set in an environment with sufficiently small noise,no cooling is necessary for the preamplifier 113. The free inductiondecay signal amplified in the two stage amplifiers is detected by adetector 115 to become a signal with a bandwidth of several kHz.Further, the signal is expanded in Fourier series to be subjected todata analysis in a signal-analyzing unit 116, by which an NMR spectrumcan be obtained.

In general, for measuring NMR spectra of nuclides different from oneanother, probe coils are required by the number equivalent to that ofnuclides to be measured. However, as described above, by taking the coil1 a as that for detecting proton and the coil in which the coil 1 b, 1 aand 1 c are connected in series as that for ¹³C, that is, by sharing thecoil 1 a, the volume of the whole coil can be reduced to have made itpossible to downsize the NMR probe coil. There are many more peripheralunits than those explained above, which are, however, omitted in FIG.11.

The inventors carried out manufacturing of the probe for an NMRapparatus as described above. The coil 1 a as a solenoid type has adiameter of 2 cm and a longitudinal length of 5 cm with a number ofturns of the coil 1 a provided as being 10 turns. While, each of thecoils 1 b and 1 c has a diameter of 2 cm and a longitudinal length of 2cm.

The coils 1 a, 1 b, and 1 c were cooled at about 10K by a gas coolingmethod using gaseous helium and the preamplifiers 103 and 113 werecooled at about 77K by a pool cooling method using liquid nitrogen. Theprobe for an NMR apparatus as described above was disposed in a highuniform static magnetic field of 2.35 T to measure an NMR spectrum ofproton in ethanol by using a high frequency power source of 100 MHz and15 MHz as the resonant frequencies of proton.

As a result of a series of tests, it was ascertained that the probe wasalmost equivalent about the S/N ratio and the Q-factor to the probeshown in Example 2 to provide sufficiently high performance.

EXAMPLE 6

In Example 6, it is characterized that a probe coil for an NMR apparatusis a magnesium diboride superconductor 11 mixed with metal, whichsuperconductor is formed on the basis of a mixture of magnesium diboridepowders and metal powders. Except for this point, this Example is almostthe same as Example 4. This brings realization of a probe coil that canaccelerate the decay of the high frequency pulsed current by adequateelectric resistance of the coil.

The probe for an NMR apparatus carries out transmission of a highfrequency pulsed magnetic field to a sample and reception of a freeinduction decay signal by the same probe. Since the free induction decaysignal must be observed immediately after the transmission of the highfrequency pulsed magnetic field, in the probe coil, the high frequencypulsed current must have been immediately decayed. When the probe coilis formed with a superconductor, however, the decay time tends to becomelonger, for which the starting time for capturing the free inductiondecay signal is inevitably delayed to cause a problem of reducing amountof the free induction decay signal data. In order to solve the problem,a slight trace of metal with some degree of normal conductivity wasadded to the superconductor, by which a slight electric resistance wasdeveloped to make it possible to accelerate decay of the high frequencypulsed current. Addable metal is copper, aluminum, nickel, silver, lead,tin, indium, or the like, effect of which can be observed with a maximumamount of addition up to several %, although the effect depends on thekind of added metal.

The inventors carried out manufacturing of the probe for an NMRapparatus as described above. The coil 1 as a solenoid type has adiameter of 2 cm and a longitudinal length of 5 cm with a number ofturns of the coil 1 provided as being 10 turns. The coil 1 was cooled atabout 10K by a gas cooling method using gaseous helium and thepreamplifier 103 was cooled at about 77K by a pool cooling method usingliquid nitrogen. The probe for an NMR apparatus as described above wasdisposed in a high uniform static magnetic field of 2.35 T to measure anNMR spectrum of proton in ethanol by using a high frequency power sourceof 100 MHz as the resonant frequency of proton. As a result of a seriesof tests, it was ascertained that the probe was almost equivalent to theprobe shown in Example 3 about the S/N ratio and the Q-factor, but thedecay time of the high frequency pulsed current was improved down to onetwentieth compared with that in Example 3.

As was described above, by adding a slight trace of metal with somedegree of normal conductivity to a supercondutor, a slight electricresistance was made developed in the coil. This enabled realization of aprobe coil for an NMR apparatus that can accelerate the decay of thehigh frequency pulse.

EXAMPLE 7

In Example 7, it is characterized that a probe coil for an NMR apparatusis formed with a single metal selected from gold, silver, copper,aluminum, iron, platinum, palladium, nickel, stainless steel, chromium,magnesium, tantalum, niobium, titanium, zinc, beryllium, tungsten, orcobalt, or an alloy including a plurality thereof. Except for thispoint, this Example is almost the same as Example 4.

The inventors carried out manufacturing of the probe for an NMRapparatus as described above. The coil 1 as a solenoid type has adiameter of 2 cm and a longitudinal length of 5 cm with a number ofturns of the coil 1 provided as being 10 turns. The coil 1 was cooled atabout 10K by a gas cooling method using gaseous helium and thepreamplifier 103 was cooled at about 77K by a pool cooling method usingliquid nitrogen. The probe for an NMR apparatus as described above wasdisposed in a high uniform static magnetic field of 2.35 T to measure anNMR spectrum of proton in ethanol by using a high frequency power sourceof 100 MHz as the resonant frequency of proton. Besides, as acomparative example, a probe with the coil 1 made of copper was alsomanufactured for measuring the NMR spectrum of proton with the coil 1and the preamplifier 103 kept at room temperature without being cooled.As a result of a series of tests, about the S/N ratio, it wasascertained that the probe using the cooled metal for the coil 1 wassuperior about three times to the probe using copper. Furthermore, itwas also ascertained that the probe was superior about ten times in theQ-factor.

As was described above, by using for a probe coil the cooled metal,realization of a probe coil for an NMR apparatus has been made possiblewith improved Q-factor and S/N ratio.

EXAMPLE 8

In Example 8, it is characterized that a probe coil for an NMR apparatusis formed with a superconductor of YBa₂Cu₃O_(7−x), Bi₂Sr₂Ca₁Cu₂O_(x), orBi₂Sr₂Ca₂Cu₃O_(x). Except for this, this Example is almost the same asExample 4.

The inventors carried out manufacturing of the probe for an NMRapparatus as described above. The coil 1 as a solenoid type has adiameter of 2 cm and a longitudinal length of 5 cm with a number ofturns of the coil 1 provided as being 10 turns. The coil 1 was cooled atabout 10K by a gas cooling method using gaseous helium and thepreamplifier 103 was cooled at about 77K by a pool cooling method usingliquid nitrogen. The probe for an NMR apparatus as described above wasdisposed in a high uniform static magnetic field of 2.35 T to measure anNMR spectrum of proton in ethanol by using a high frequency power sourceof 100 MHz as the resonant frequency of proton. Besides, as acomparative example, a probe with the coil 1 made of copper was alsomanufactured for measuring the NMR spectrum of proton with the coil 1and the preamplifier 103 kept at room temperature without being cooled.As a result of a series of tests, about the S/N ratio, it wasascertained that the probe using the superconductor of YBa₂Cu₃O_(7−x),Bi₂Sr₂Ca₁Cu₂O_(x), or Bi₂Sr₂Ca₂Cu₃O_(x) for the coil 1 was superiorabout three to ten times to the probe using copper. Furthermore, it wasalso ascertained that the probe was superior about five to twenty timesin the Q-factor.

As was described above, by using for a probe coil the superconductor ofYBa₂Cu₃O_(7−x), Bi₂Sr₂Ca₁Cu₂O_(x), or Bi₂Sr₂Ca₂Cu₃O_(x), realization ofa probe coil for an NMR apparatus has been made possible with improvedQ-factor and S/N ratio.

As described above, a probe coil for an NMR apparatus can be providedwhich can transmit and receive high frequency radio waves with improvedQ-factor and S/N ratio.

1. A probe coil for an NMR apparatus comprising a plurality of coilsusing a magnesium diboride superconductor, wherein the coil using saidmagnesium diboride superconductor is of a saddle type.
 2. A probe coilfor an NMR apparatus according to claim 1, wherein a plurality of saidcoils are connected by using a material including magnesium diboride. 3.A probe coil for an NMR apparatus according to claim 1, wherein the coiluses a magnesium diboride superconductor mixed with a metal.
 4. Theprobe coil for an NMR apparatus according to claim 1, wherein the coilcontains one of gold, silver, copper, aluminum, iron, platinum,paradium, nickel, stainless steel, chromium, magnesium, tantalum,niobium, titanium, zinc, beryllium, tungsten, cobalt, and alloysincluding the above elements.
 5. The probe coil for an NMR apparatusaccording to claim 1, wherein said magnesium diboride superconductor isexposed on an outer surface of said coil for the NMR.